Method of producing hydrogenated hydrocarbon products



Jan. 27, 1942. R. LEPREsTRE 2,271,017

METHOD OF ERODUCING HYDROGENATED HYDROCARBON PRODUCTS Filed May 10, 19582' Sheets-Sheet l Jan. 27,- 1942. R. LEPRESTREI METHOD OF PRODUCINGHYDROGENATED HYDROCARBON PRODUCTS Filed May 10, 1938 2 Sheets-Sheet 2WII IZ UTLET 7 m y mm m m a 7 00m 2 2 mm I 1 5 34 u w I: A !|l l i 7 l rE R R 2 mf 5 WW a J 2 MTZ r o 7% E ml. L r MW AU L H 0 Q COLLOID 3wvwwtpfl Patented Jan. 27, 1942 METHOD OF PRODUCING HYDROGENATEDHYDROCARBON PRODUCTS Rene Leprestre, New York, N. Y.; Margaret 0.

Leprestre,. H. Douglas Hadden, Ralph C. Tobin, and Joseph Dannenberg,executors of the estate of said Leprestre, deceased, assignors toApplied Chemicals", Inc a corporation of Delaware Application May 10,1938, Serial No. 207,095

-1 Claim. (Cl. 196-53) This invention relates to a method of treatingcomplex high boiling hydrocarbon mixtures and bituminous materials underhydrogenating conditions to produce hydrogenated products generally oflower boiling point than the original material.

Cracking processes now commonly practiced yield volatile productsincluding motor fuels and also high boiling black residual oils commonlycalled tars. Both the lighter oils and the residual tarry oils aredeficient'in hydrogen, and in the case of the residual oils furthercracking results mainly in the formation'of coke. Such residual oils areusually disposed of as low grade fuel oils.

The present process accomplishes the conversion of heavy residual oilsand bituminous materials deficient in hydrogen into reaction prod-' uctswhich are more fully saturated with respect to hydrogen, such reactionproducts ineluding motor fuel of high octane value and which is muchmore stable than the cracked gasolines produced by ordinary crackingprocesses. This is accomplished through the use of a catalyst for thehydrogenation of the hydrocarbons, in the presence of hydrogen or asubstance which may yield hydrogen under the conditions of the .proc-'ess, the reactions taking place under the combined action of heat andpressure. The heavy high boiling oil or bituminous material is highlyemulsified with water, to which a smallproportion of an alcohol may beadded for the purpose of stabilizing the oil-water emulsion.

A primary object of the invention is to make motor fuel of high octanevalue.

Accordingly, to accomplish these purposes I have invented a new andnovel process forenriching with hydrogen heavy petroleum oils,

cracked oils and residual oils, tars and bituminous substancesgenerally; which process consists essentially in first mixing thehydrocarbon material to be enriched with water, reducing the oil orbituminous material to a fine state of subdivision, including, whennecessary, reduction to 1 different for each grade of hydrocarbonproduct desired. V I

A further object is to provide a novel apparatus which includes valvemeans for accurately controlling the escape of gas from the retortthereby not only controlling the pressure, but, at the same timeinsuring more or'less prolonged contact between the gas and thecatalyzer to obtain hydrocarbons of different hydrogen content.

I have further devised for use with either of these'forms of myapparatus, means, for heating the chamber or retort, and means forpreheating, by either heat recovery or direct application of heat, thehydrocarbon mixture, and the hydrogen or hydrogen carrier, before theyare injected into the retort or the reaction cylinder.

And I have further devised means for atomizing and mixing the finelydivided hydrocarbon and hydrogen or hydrogen carrier; upon theirinjection into the retort or cylinder and in the:

presence of the ca'talyzer.

A still further object is to provide simple and expeditious means forrenewing the catalytic element when its efficiency has been reduced bycontinued operation.

With the above and other objects in view which will more readily appearas the nature of the invention is better understood, 'the same consistsin the novel procedure and apparatus hereinafter more fully set forthand claimed.

While the method'may be carried out in various types of apparatus,nevertheless, a preferred form is shown in the accompanying drawings, in

I which Figure l is a vertical sectional view of the retort.

Figure 1 is a diagrammatic side'elevation'of the complete retort.

Figure 2is an enlarged detail sectional view of the upper portion of theretort.

Figure 3 is an enlargedvertical sectional view of the bottom of theretort.

Figure 4 is a diagrammatic view of the preferred arrangement of nozzlesfor the hydrogen and the colloidal solution.

Incarrying out the invention, the first step is to prepare an aqueousmixture of the hydrocarbon base material to be hydrogenated, and toincorporate in the mixture a small percentage of a suitable emulsionstabilizer, such, for instance, alcohol.

The hydrocarbon, water and alcohol are emulsified in suitable colloidmills to reduce the entire mass completely to its colloidal state. Thiscolloidal emulsion is then heated under pressure to approximately 1000to 1200 F. and pumped under high pressure, according to the material tobe treated, into the reaction chamber through opposed nozzles sodirected that the jets impinge upon each other; The chamber pressurewill be that required for the conversion of the particular mixture intothe desired hydrocarbon fraction and the pump pressure must besufiiciently higher than this to insure sufficient jet velocity to breakthe mixture up into fine spray. Water gas or hydrogen is also injectedinto the chambers through another pair of opposed nozzles set in thesame plane as the mixture nozzles and so set that the jets impinge bothon each other and on the points of impact of the mixture jets. Thepressure of the hydrogen is determined by the same considerations asthose determining the pressure of the mixture. Both the mixture and thehydrogen reach the nozzles through pipe coils contained in the upper endof the retort hieue which the ente ing m x r a pre-heated to any desireddegree, according to t e ma erial to h treated ess han he re emp rat resan simiiitah eusly the t gases rom he reterare eccl si- T e ixtu e ofspray a d et i-re h he e les pass upw rdly th ou h he eto t an e thus cari d h o gh the ca a y ic ma er al and, d to the eombinatiens o ressuretemp u and actio o he a al st th emi a e tions are co p e ed to p oducehydrocarbon fractions of the desired eem si ie Preparatory to star n theretor t i o ht p to the desired tempe ature by the use of t e t n o l inthe l wer sect on o he re o After the reactions have started, an dde heaequired by the e mbinaiien of the chemi al reactions is supplied throughthe heating coil.

Referring to the drawinaa, it will be obherved that the retort includesa suitable column or casins I provided at its uppe end with the fl n eportion 2 for facilitating the securing of a cap or cover structure Cthereto by the use of suitable bolts 3, while the bottom of the columnis provided with the flange 4 which piiov-ides adequate means foranchoring a base plate .5 thereto by the bolts 6 or equivalentfastenings.

The lower portion .of the casing l is lined with suitable refractorymaterial surrounding an electrical heating element in the form of anannular member 8 which provides a mixing or impinging chamber M as willlater appear. The heating element 8 has the electrical wires 9 coiledabout its outer face so that the inner face thereof presents a smoothunbroken surface. The electrical connections for the heating wires 9 maybe made through the conduit 9a (Fig. 3) in the base plate 5. The lowerportion of the heating element 8 is embedded in the horizontal layer ofrefractory material I covering the inner face of the base 5, and, atthis point, it may be noted that the said base is suitably constructedto provide for the insertion of one or more pyrometers P and P and apressure gauge G The cap structure 0 carries therewith suitable pipes l2and II for supplying the hydrogen and the mixture or colloid to theretort, and also carries the catalytic unit A so that when the bolts 3have been disconnected from the flange 2, the entire cap structure C andits associated parts may be lifted bodily out of the retort by the useof a crane or other suitable lifting apparatus. In that connection, itwill, of course, be understood that the pipes I I and H whichrespectively supply the mixture or colloid and the hydrogen are providedwith suitable joints which may be disconnected when it i desired to liftthe cover C from the retort of the casing I.

The catalyst A, (for example) iron oxide, is contained in a basket #3having a foraminous bottom wall l3 engaged and supported by the head I4of a rod [5 when the cover structure C is removed from the casing. Inthat connection, however, it will be observed that the said bottom walll3 of the basket may rest upon the annular abutment 8 of the heatingelement when the basket is in use as shown in Figure 1. That is to say,the upper end of the rod !5 extends through a strap or bracket [6carried by the cover structure and the nut I! on the rod is preferablyso positioned that the cover will have a certain amount of play relativeto the rod, thus insuring the proper degree of tolerance to permit thebasket to rest on the annular abutment 8*, of'the heating element, andat the sam tim p mit he over s ructure includin the pla Ci e flus l seaon the flan he, f am nous b s et wh ch. ho h eatalyz r A is surroundedby refractory blocks I3 which may have lateral expansion passagestherebetween.

Refer-ring further to the cap or cover structure C, it is pointed outthat the mixture pipe ll carried by the cover is formed internally ofthe retort, that is, within what may be termed a gas collecting chamber,or a preheating chamber N, with a mixture preheating coil H andlikewise, the portion of the hydrogen pipe I2 at the underside of thecover C is formed into a hydrogen preheating coil [2 so that. both themixture pipe. and the hydrogen pipe are coiled within the upper portionof the retort above the catalyzer unit A. The lower end ill of themixture pipe extends through the catalyzing material A in the basket l3and projects into the mixing chamber M where it is provided with thehorizontal branch pipev II which is preferably of arcuate formation(Fig. 4) and provided with diametrically disposed nozzle portions Hforming jets disposed in opposed relation toward the axis of the mixingchamber M so that high pressure streams of mixture issuing from oppositejets impinge upon each other, in the mixing T chamber, while the deviceis in operation.

Similarly, the lower portion of the hydrogen pipe below the coil lZe isprovided with an extension l2 which passes through the catalyzingmaterial A in the basket l3 and thence through lthe bottom of the basketinto the mixing chamnd hydro en ch mpi e on ach o er at he a of h mi gamber a the ame tim n b aus of he hi h ressure a which th x ur nd h droen a e discharged again each. o h r h are h rou hly mixed r broken e ttheir p n o on act mix ure,

forces itself through the catalyzing chamber upward into the chamber Nat the upper end of the retort, said chamber containing the preheatingcoils ll and I2, respectively for the colloid mixture and the hydrogen.

When the gasesreach' the top of the chamber N they have given upconsiderable heat to the coils ll and 12?, and'therefore they areconsiderably. lowered in temperature as. compared with the heat in themixing chamber.

From the chamber N the products pass through a valve orifice whose areamay be accurately controlled and predetermined to permit obtainingdifferent qualities of hydrocarbon distillate. That is to say, if it isdesired to produce, for example, high octane gasoline, the valve orificeis set to produce atvery small or limited clearance which has the effectof keeping all of the mixture in the retort longer, thus subjecting themto prolonged contact with the catalyzer to insure morethorough union ofthe hydrogen and hydrocarbon vapors. On the other hand, if it isintended to produce low octane hydrocarbon products'the valve orificemay be opened Wider or, in other words, a greater outlet area orclearance maybe provided which will allow the products to escape quickerfrom the retort and hence with a shorter period of contact with thecatalyzer.

Referring to Figure 2 it will be apparent that the gases in the chamberN are permitted to pass therefrom to the condenser (not shown) throughthe valve orifice I3 which operates in conjunction with a valve head l9formed at one end of hollow stem 20. This stem has external threads 2|so that when it is turned or rotated by the hand wheel 22, the positionof the valve head l9 may be varied relative to the seat l8. As theproducts pass between the valve seat I8 and the head IE! it enters achamber 23 in the cover, the aid chamber being connected to an outlettube 24 leading to a condenser. The hollow stem 20 of the valve assemblyis provided with a water inlet pipe 25 whose discharge end extends inclose proximity to the valve head l9, and a water takeoif connection 26is provided for the hollow stem 20 above the hand wheel. Also, it willbe seen that a suitable packing 27 is provided about the hollow valvestem 20 above the chamber 23 and below the screw threads 2|. However, tofully utilize any gas that may escape past the' packing 21, there isprovided above said packing a trap chamber 28 which in turn is providedwith a take-off 29 leading to the condenser. The packing 21 ispreferably in the form of a spool thus enabling a water jacket to beformed about the medial portion of the valve stem 20, the said jacketbeing provided with a water inlet connection 30 and a water outlet 3|.In addition, the face of the cover exposed to the gases within thechamber N may be provided with a water jacket 32, suitable inlet andoutlet connections being provided for the purpose.

Theupper outer portion of the column i in the zone of the chamber N mayalso be provided with a water jacket 33, the said jacket being providedwith a water inlet connection 34 and an outlet connection 35.

Referring to the general operation of the ap paratus and the severalstages of the process performed therein, it is pointed out that thehydrocarbon base material, in finely divided or colloidal form, ispumped or introduced into the retort through the supply connection I I.The hydrocarbon mixture then proceeds through the preheating coil II,and thus becomes heated as it flows downwardly toward the mixing chamberM through the pipe extension I I When the preheated hydrocarbon mixturereaches the branch pipe II, it is'forced through opposed branch nozzlesI I thus forming opposing mixture'jets which impinge upon each otherwithgreat force at approximately the axis of the mixing chamber M. I

Simultaneously, "with the introduction of the hydrocarbon mixture intothe retort, hydrogen gas'entersthe pipe l2 and then passes through thepreheating" coil I2 and pipe section l2 to the branch connection I2whereupon the hydrogen is discharged through the opposed nozzles 12, injet form, not only to cause the hydrogen jets to'impinge upon themselvesbut to also impinge upon the hydrocarbon mixture jets disapproximately1000 F., in the example now. given,

by the electric heating element 9. Thus, when the hydrogen and thehydrocarbon'mixture are pumped into the mixing. chamber at a uniformpressure as above indicated the resultant mixture is forced upwardlythrough the bed of catalyst in the basket l3.

After the mixture is transformed into new products by the catalyst itpasses through the chamber N, which, as previously explained, is

entirely closed except for the valve l8-l9 which is definitely andaccurately set at a predetermined clearance. If the valve is so adjustedas to hold back the gases in the chamber N, or in other words, if thevalve is set with only a comparatively small opening, it will beapparent that the gases are held for a prolonged period of contact withthe catalyst to produce a motor fuel having a higher content ofhydrogen, and a high octane value, i. e. viz. to 98 octane number.

Taking one example, as an illustration, if it is desired to produce alower grade gasoline (68 to '70 octane) it is necessary to open thevalve Wider, and also change the pressure and the quantity of hydrogen.In this example, the pressure of hydrogen and hydrocarbon mixture may belowered to from 5000 to 8000 pounds, and the temperature maintained inthe mixing chamber at approximately 1000 F. While the process has beenoperated at temperatures from approximately 900 F. to 1150 F. it isobvious to those skilled in the art that varying both temperature and,or, pressure will result in the formation of different hydrocarbons. Itis likewise obvious that the high limits are governed by theconstruction of the reaction chamber.

The mixing and impinging chamber M may be accurately checked as totemperature through the medium of pyrometers P and P located substan--tially at the axis of the mixing chamber and near the wall thereof sothat the temperature can be maintained at the desired degree under allconditions of use. Moreover, through the medium of the pressure gage Gthe pressure in the mixing chamber may be accurately checked so that theoperating pressure at all times may be controlled through themanipulation of the valve I8I9. As previously indicated, the pressure ofboth hydrogen and hydrocarbon mixture are always uniform in any givenexample, according to the product desired, and a suitable automaticproduce a new mixture.

sure rise that mayoccur therein.

The products of the reactions occurring in the catalyst chamber may bereleased to atmospheric pressure by the control valve I8-l9 and thevapor mixture thus produced cooled and condensed by conventional meansand any residual gases subsequently separated. It .Will"-b e understood,however, that cooling andcondensationof the products maybe carried outunder pressure, if desired; such pressures would ordinarily belbelow theoperating pressuresof the catalyst chamber. Condensation of the productsundermoderate pressures has the advantage of retaining very volatilehydrocarbons in the condensate. However, the means employed forcondensation of motor fuels and the like are well understood in the artand are not a part ofmy invention.

From the'foregoing it will be apparent that'the distinctive features ofthe present invention reside in the provision of a heated mixing,chamber into which hydrocarbon mixtureand hydrogen may be injected andmixed in the presence of controlled heat, pressure, and watergas therebyto This mixture forces .its way through the catalyst containing basket[3 relief valve of any approved type :may be zplaced in any convenient:location to provide for ,relief of theretortfrom any excessive'orabnormaljpreswhich brings about the :complete :union :of "theconstituents and Iforms new reaction'products.

Inasmuch as the-colloid and watert gas supply pipes, andwtheir coils,are carried *by the cover, and the catalyzer basket I3 is also:connected to the cover, it will-be apparent that the entire interiorassembly 0f the retort may rbe removed when desired, or-w'hentheca'talyzer requires removal.

I claim: A process for increasing the hydrocarbon contained and causing:the said .base material :and hydrogen carrier to brought into directimpingement at a common focal point in thetsaid heatedchamber,-.-circulating the mixture formed in said chamber at apredetermined speed by'a'nd in contact with a catalyst, andsubsequently-cooling and condensing the gaseous products resulting fromthe catalytic *reaction.

RENE LEPRESTRE.

